The phthalimide N-oxyl (PINO) radical was generated by the oxidation of N-hydroxyphthalimide (NHPI) with Pb(OAc) 4 in acetic acid. The molar absorptivity of PINO • is 1.36 × 10 3 L mol - 1 cm - 1 at λ max 382 nm. The PINO radical decomposes slowly with a second-order rate constant of 0.6 ± 0.1 L mol - 1 s - 1 at 25 °C. The reactions of PINO • with substituted toluenes, benzaldehydes, and benzyl alcohols were investigated under an argon atmosphere. Pc optimizer freeware. The second-order rate constants were correlated by means of a Hammett analysis. The reactions with toluenes and benzyl alcohols have better correlations with σ + (ρ = −1.3 and −0.41), and the reaction with benzaldehydes correlates better with σ (ρ = −0.91).

Nov 2, 2016 - PDF. Abstract; 1 Introduction and Scope; 2 Fundamentals. It discusses methods for the determination of the reaction order. Reaction mechanism came and still comes from chemical kinetics. The reactive form of the biopolymer is not free cellulose but cellulose hydrogen bonded to the IL.

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The kinetic isotope effect was also studied and significantly large values of k H/ k D were obtained: 25.0 ( p-xylene), 27.1 (toluene), 27.5 (benzaldehyde), and 16.9 (benzyl alcohol) at 25 °C. From the Arrhenius plot for the reactions with p-xylene and p-xylene- d 10, the difference of the activation energies, E a D − E a H, was 12.6 ± 0.8 kJ mol - 1 and the ratio of preexponential factors, A H/ A D, was 0.17 ± 0.05. These findings indicate that quantum mechanical tunneling plays an important role in these reactions.